WO1999029936A1 - Procede d'extrusion de fibres - Google Patents

Procede d'extrusion de fibres Download PDF

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Publication number
WO1999029936A1
WO1999029936A1 PCT/US1998/025517 US9825517W WO9929936A1 WO 1999029936 A1 WO1999029936 A1 WO 1999029936A1 US 9825517 W US9825517 W US 9825517W WO 9929936 A1 WO9929936 A1 WO 9929936A1
Authority
WO
WIPO (PCT)
Prior art keywords
fiber
hydrophilicity imparting
fluorochemical
imparting compound
spin
Prior art date
Application number
PCT/US1998/025517
Other languages
English (en)
Inventor
Bart Goeman
Original Assignee
Minnesota Mining And Manufacturing Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US09/554,528 priority Critical patent/US6426025B1/en
Application filed by Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Priority to DE69817014T priority patent/DE69817014T2/de
Priority to JP2000524501A priority patent/JP2001526326A/ja
Priority to AU16175/99A priority patent/AU742193B2/en
Priority to EP98960619A priority patent/EP1036223B1/fr
Publication of WO1999029936A1 publication Critical patent/WO1999029936A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Definitions

  • the present invention relates to fiber production and fiber treatment that renders fiber soil resistant, oil repellent, and/or water repellent.
  • spin finish including a spin oil is a lubricating composition deposited on the surface of the fiber to reduce the fiber-fiber friction and the friction developed as the yarn passes over the metal machinery surfaces.
  • Spin oil typically contains a large number of chemical components, the major components being lubricant, antistatic agent and emulsifier.
  • the amount of spin finish needed depends on the producer and manufacturing process, and typically the residual spin finish on the fiber varies between 0.7% and 5%.
  • a major disadvantage of the use of a spin finish that includes a spin oil is that residues of the finish on the extruded fiber attract soil. It also decreases the efficiency of any protective treatment applied to the fiber and as such reduces the soil resistance of the finished products.
  • Fluorochemical compositions are commercially used for this purpose. They can be applied to various substrates by methods which include, for example, spraying, foaming, padding, and finish bath immersion.
  • U.S. Patent No. 4,264,484 discloses a liquid ca ⁇ et treating composition containing a water-insoluble addition polymer that is derived from polymerizable ethylenically unsaturated monomer that is free of non-vinylic fluorine and has at least one major transition temperature higher than about 25°C, and a water-insoluble fluoroaliphatic radical- and aliphatic chlorine-containing ester having at least one major transition temperature higher than about 25°C.
  • U.S. Patent No. 4,107,055 discloses a fabric coating composition, including a polymer having a glass transition temperature above room temperature, an ionic fluorinated surfactant and a carrier.
  • U.S. Patent No. 4,043,964 discloses a coating which provides a durably soil- resistant carpet and which contains: (a) at least one phase of a specified, water-insoluble addition polymer derived from a polymerizable ethylenically unsaturated monomer that is free of non-vinylic fluorine, and (b) at least one phase of a specified, water-insoluble fluorinated component containing a fluoroaliphatic radical of at least 3 carbon atoms.
  • the monomer from which the fluorinated component is formed may contain dicarboxylic acid, glycol, diamine, hydroxyamine, etc.
  • a common feature of the treating or coating compositions disclosed in the above- mentioned U.S. patents is that they are to be applied to the carpet or fabric after its production in a separate treating step.
  • the application equipment and time required for such a treating step adds to the cost of the final product.
  • Textile fibers and yarns can also be treated by inco ⁇ oration of a fluorochemical repellent treating agent in the spin finishing bath, for example, as disclosed in U.S. Patent Nos. 4,190,545 and 4,192,754.
  • a drawback of such a process is the formation of deposits on the rolls caused by sedimentation of the fluorochemical oil- and water- repellent agent/spin finish mixture. The deposit on the rolls can cause fiber breaks and must be removed frequently. This is time consuming and expensive and is no longer accepted as an application method by fiber manufacturers.
  • the more spin finish added to the fluorochemical treating agent the more roll build up occurs, and the greater the reduction in repellent properties of the finished product because of the high level of spin oil present on the treated substrate.
  • treated textile fibers and yarns can be obtained by melt extrusion of a blend of a synthetic fiber-forming polymer and a fluorochemical composition.
  • melt extrusion is described for example in U.S. Patent No. 3,839,312.
  • This patent discloses that soil and stain repellency of extruded filaments of a synthetic resin can be improved by inco ⁇ orating in the resin a small amount, about 1 percent, of an amphipathic compound having from one to four fluoroalkyl groups pendent from an organic radical.
  • the repellency is provided by the fluoroalkyl groups, which tend to be concentrated at the surface of the fiber.
  • WO 92/18569 and WO 95/01396 disclose permanently soil resistant polymeric compositions such as fibers and yarns that have a fluorochemical dispersed throughout the polymer. These polymer compositions are prepared by melt extrusion of the fluorochemical with the desired polymer. Polymers that can be used with the fluorochemical include polyester, polypropylene, polyethylene and polyamide.
  • U.S. Patent No. 5,025,052 discloses certain fluoroaliphatic group-containing oxazolidinone compositions.
  • the patent also discloses fibers, films, and molded articles prepared, for example, by injection molding a blend or mixture of fiber-or film-forming synthetic organic polymers and certain fluorochemical oxazolidinones.
  • the resulting fibers, films, and molded articles are said to have low surface energy, oil and water repellency, and anti-soiling properties.
  • European Pat. Pub. No. 0 516 271 discloses durably hydrophilic thermoplastic fibers comprising thermoplastic polymer and fluoroaliphatic group-containing non-ionic compounds.
  • Fluorochemical hydrophilicity imparting compounds are disclosed as preferred hydrophilicity imparting compounds. It is taught that as a result of the use of the hydrophilicity imparting compound in the filaments of the yarn, less or no spin oil is needed in the spin finishing bath and as a result, the ca ⁇ et is less prone to soiling. Although this method is successful, the oil and/or water repellency properties of the obtained fibers is generally poor and there continues to be a desire to improve the soil repellency properties.
  • the invention provides a process for obtaining a fiber comprising the steps of: melt extruding a mixture of thermoplastic polymer and hydrophilicity imparting compound to form a plurality of filaments; applying a spin finish to said filaments; and spinning said filaments into a fiber; wherein said spin finish comprises fluorochemical.
  • the fluorochemical is an effective oil and/or water repellent and it imparts good oil and water repellency properties to the fiber.
  • the invention provides a fiber containing a plurality of filaments of a thermoplastic polymer having dispersed therein hydrophilicity imparting compound characterized in that the filaments comprise on at least part of their surface fluorochemical.
  • the fluorochemical preferably is an effective oil and/or water repellent treatment and it imparts good oil and water repellency properties to the fiber.
  • the invention provides a ca ⁇ et or textile comprising such fibers.
  • Thermoplastic polymers useful in the invention include fiber-forming poly(alpha)olefins, polyesters and polyamides.
  • Preferred thermoplastic polymers are poly (alpha)olefins.
  • Poly(alpha)olefins useful in the invention can include the normally solid, homo-, co- and te ⁇ olymers of aliphatic mono- 1 -olefins (alpha olefins) as they are generally recognized in the art.
  • the monomers employed in making such poly(alpha)olefins contain 2 to about 10 carbon atoms per molecule, although higher molecular weight monomers sometimes are used as comonomers. Blends of the polymers and copolymers prepared mechanically or in situ may also be used.
  • Examples of monomers that can be employed in the invention include ethylene, propylene, butene-1, pentene-1, 4-methyl- pentene-1, hexene-1, and octene-1, alone, or in admixture, or in sequential polymerization systems.
  • thermoplastic poly(alpha)olefin polymers examples include polyethylene, polypropylene, propylene/ethylene copolymers, polybutylene and blends thereof.
  • Polypropylene is particularly preferred for use in the invention.
  • Hydrophilicity imparting compounds useful in this invention may be fluorochemical or non-fluorochemical, mixtures of such compounds or mixtures of fluorochemical compounds and non-fluorochemical compounds.
  • Non-fluorochemical hydrophilicity imparting compounds are substantially free of fluorine (preferably containing less than about 10 % by weight and more preferably less than about 5% by weight of fluorine) and are generally hydrophilic in nature or contain at least a sufficient number of hydrophilic moieties such that hydrophilicity or wettability is provided to the surface of the thermoplastic polymer filaments. Included are low molecular weight compounds, oligomers and polymers. Suitable non-fluorochemical hydrophilicity imparting compounds are preferably incompatible with the thermoplastic polymer melt and are preferably stable at the required extrusion temperatures.
  • Suitable non-fluorochemical hydrophilicity imparting compounds can be anionic, cationic, non-ionic or amphoteric. Preferred compounds include compounds which are known to have utility as surfactants. Particularly preferred non-fluorochemical hydrophilicity imparting compounds are those that contain at least one poly(oxyalkylene) group. Fluorochemical hydrophilicity imparting compounds useful in the invention are hydrophilic in nature and can include compounds, oligomers, and polymers. Such materials will contain at least about 10% by weight of fluorine (i.e., carbon-bonded fluorine). They contain one or more fluorochemical radicals (R ), and one or more water solubilizing polar groups (Z), which radicals and groups are usually connected together by suitable linking groups (Q).
  • fluorine i.e., carbon-bonded fluorine
  • R fluorochemical radicals
  • Z water solubilizing polar groups
  • the fluorochemical radical, Rf, in the fluorochemical hydrophilicity imparting compound can be generally described as a fluorinated, preferably saturated, monovalent radical of at least about 4 carbon atoms.
  • the fluorochemical radical is a fluoroaliphatic, non-aromatic radical.
  • the aliphatic chain may be straight, branched, or, if sufficiently large, cyclic, and it may include oxygen, di- or hexavalent sulfur, or trivalent nitrogen atoms bonded only to carbon atoms.
  • a fully fluorinated radical is preferred, but hydrogen or chlorine atoms may be present as substituents provided that no more than one atom of either is present for every two carbon atoms.
  • Fluoroaliphatic radicals containing about 5 to about 12 carbon atoms are most preferred.
  • the water solubilizing polar group or moiety, Z, of fluorochemical hydrophilicity imparting compound can be a non-ionic, anionic, cationic, or amphoteric moiety, or combinations of said groups or moieties which may be the same or different.
  • the water solubilizing group comprises a poly(oxyalkylene) group, (OR')x, where R' is an alkylene group having 2 to about 4 carbon atoms, such as -CH 2 CH 2 -, -CH CH 2 CH 2 -, -CH(CH 3 )CH 2 -, and -CH(CH 3 )CH(CH 3 )- or mixtures thereof, and x is an integer from about 6 to about 20.
  • the oxyalkylene units in said poly(oxyalkylene) may be the same, as in poly(oxypropylene), or present as a mixture, such as in a heteric, straight or branched chain of randomly distributed oxyethylene and oxypropylene units (e.g., poly(oxyethylene- co-oxypropylene), or as in a straight or branched chain of blocks of oxyethylene units and blocks of oxypropylene units.
  • the poly(oxyalkylene) chain can be interrupted by or include one or more catenary linkages, providing such linkages do not substantially alter the water- solubilizing character of the poly(oxyalkylene) chain.
  • the Z group is terminated with hydroxyl or lower alkyl ether for example, -OCH 3 or -OCH 2 CH 3 .
  • Typical anionic groups include CO 2 H, CO 2 M, SO 3 H, SO 3 M, OSO 3 H, OSO 3 M, OPO(OH) 2 , and OPO(OM) 2 , where M is a metallic ion (such as sodium or potassium), or ammonium ion, or other amine cation.
  • Typical cationic groups include NR 3 + A " , where R is a lower alkyl group such as methyl, ethyl, butyl, hydroxyethyl or hydrogen and A is an anion such as chloride, sulfate, phosphate, hydroxide or iodide.
  • Typical mixed or amphoteric groups would include N CH zC ⁇ HtCOO " , N + (CH 3 ) 2 C 3 H 6 SO 3 " or an amine-oxide.
  • the linking group, Q is a multivalent, generally divalent, linking group such as alkylene, arylene, sulfonamidoalkylene, carbonamidoalkylene, and other heteroatom- containing groups such as siloxane, including combinations of such groups.
  • more than one fluoroaliphatic radical may be attached to a single linking group.
  • a single fluoroaliphatic radical may be linked by a single linking group to more than one polar solubilizing group.
  • Q can also be a covalent bond.
  • a particularly useful class of fluorochemical hydrophilicity imparting compounds are represented by the formula
  • Rf is said fluoroaliphatic radical
  • Q is said linking group
  • Z is said water solubilizing group
  • Hydrophilicity imparting fluorochemical non-ionic compounds useful in the present invention can be prepared using known methods such as those described in U.S. Patent No. 2,915,554 (Albrecht et al.).
  • the Albrecht patent discloses the preparation of fluoroaliphatic group-containing, non-ionic compounds from active hydrogen containing fluorochemical intermediates, such as fluoroaliphatic alcohols, e.g.
  • R f C ⁇ OH acids e.g., R f SO 2 N(R")CH 2 COOH, and sulfonamides, e.g., R f SO 2 N(R")H
  • R f C 2 H O(C 2 H O) intimateH
  • R f SO 2 N(R")CH 2 CO 2 (C 2 H 4 O) intimateH
  • R SOzNC ' ⁇ CzEUO R f C ⁇ OH
  • Analogous compounds can be prepared by treating the intermediates with propylene oxide or a mixture of ethylene oxide and propylene oxide.
  • hydrophilicity imparting compound is typically added in amounts between about 0.05 and about 5% by weight, preferably between about 0.5 and about 1.5% by weight, based on the total weight of thermoplastic polymer.
  • hydrophilicity imparting compounds include: C 8 Fi 7 SO 2 N(C 2 H5)CH 2 CH 2 O(CH 2 CH 2 O) 7 CH 3
  • a fiber or yarn can be produced in accordance with the invention by providing a mixture comprising thermoplastic polymer and one or more hydrophilicity imparting compounds. This mixture can be extruded to form filaments which are then preferably cooled. The bundle of filaments is then typically treated in a spin finish bath. After receiving the spin finish treatment, the filaments are generally stretched. Stretching may be accomplished over a number of rolls that are at elevated temperature sufficient to soften the thermoplastic polymer. By rotating the rolls at different speeds, stretching of the filaments can be obtained. While stretching can be accomplished in one step, it may be desirable to stretch the filaments in two steps. Typically, the filaments will be stretched 3 to 4 times the extruded length. Subsequent to stretching, and in order to obtain a ca ⁇ et yarn, it will often be desirable to texture the yarn with pressured air at an elevated temperature or steam jet and to subject it to an entanglement.
  • the spin finish comprises fluorochemical.
  • fluorochemical is an effective oil and/or water repellent.
  • the amount of fluorochemical in the spin finish will be between about 0.1% by weight and about 5% by weight, preferably between about 0.5% by weight and about 3% by weight.
  • the fluorochemicals useful in the invention include any of the known fluoroaliphatic radical-containing agents useful for the treatment of fabrics to obtain oil and water repellency. Fluorochemical radical-containing agents such as condensation polymers like polyesters, polyamides or polyepoxides, and vinyl polymers like polyacrylates, polymethacrylates or polyvinyl ethers are generally effective choices.
  • fluorochemical radical-containing agents such as condensation polymers like polyesters, polyamides or polyepoxides, and vinyl polymers like polyacrylates, polymethacrylates or polyvinyl ethers are generally effective choices.
  • Such known agents include, for example, those described in U.S. Patent Nos. 3,546,187, 3,544,537,
  • useful fluoroaliphatic radical-containing water and oil repellency imparting agents include those formed by the reaction of perfluoroaliphatic glycols or thioglycols with diisocyanates to provide perfluoroaliphatic group-containing polyurethanes. These products are normally applied to fibers as aqueous dispersions. Such reaction products are described, for example, in U.S. Patent No. 4,054,592.
  • Another group of useful fluorochemicals are fluoroaliphatic radical-containing, N-methylol condensation products. These compounds are described in U.S. Patent No. 4,477,498.
  • fluorochemicals include fluoroaliphatic radical containing polycarbodiimides which can be obtained, for example, by reaction of perfluoroaliphatic sulfonamido alkanols with polyisocyanates in the presence of suitable catalysts.
  • the fluorochemical can be a copolymer of one or more fluoroaliphatic radical- containing acrylate or methacrylate monomers, and one or more fluorine-free (or hydrocarbon) terminally ethylenically-unsaturated comonomers.
  • the preferred monomers to copolymerize with the above-described fluoroaliphatic radical-containing monomers include those selected from the group consisting of octadecylmethacryate, 1,4-butanediol diacrylate, laurylmethacrylate, butylacrylate, N- methylol acrylamide, isobutylmethacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, vinylchloride and vinylidene chloride.
  • the relative weight ratio of the fluoroaliphatic monomer(s) to the hydrocarbon co-monomer(s) can vary and is taught in the art.
  • fluorochemicals include, for example, fluorinated group containing urethanes, ureas, esters, amines (and salts thereof), amides, acids (and salts thereof), carbodiimides, guanidines, allophanates, biurets, oxazolidinones, and other substances containing one or more fluorinated groups, as well as mixtures and blends thereof.
  • Such agents are well known to those skilled in the art, see e.g., Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Vol. 24, pp. 448-451 and many (
  • the spin finish typically also includes any conventional spin oil used on extruded thermoplastic polymers.
  • the spin finish may be aqueous without any spin oil.
  • the spin finish can be applied using methods known in the art.
  • One example includes kiss roll application. The lower part of the kiss roll dips in the finish bath, while the yarn tangentially moves over the top part.
  • the add-on level of spin oil can be varied by changing several parameters, such as the geometry between yarn and roll, roll speed and the concentration of spin oil in the spin finishing bath.
  • the parameters will be adjusted so that the residual amount of spin oil on the filament will be between about 0.01% and about 1.2% by weight, preferably between about 0.01% and about 0.6% by weight, based on the total weight of filaments and spin oil. Most preferably, the residual amount of spin oil will be less than about 0.4%.
  • the water repellency of substrates was measured using a series of water-isopropyl alcohol test liquids. The water repellency of the substrates are expressed in terms of the "WR" rating.
  • the WR rating corresponds to the most penetrating test liquid that did not penetrate or wet the substrate surface after 15 seconds exposure to the substrate. Substrates penetrated by or resistant to 100% water (0% isopropyl alcohol), the least penetrating test liquid, were given a rating of 0. Substrates resistant to 100% isopropyl alcohol (0% water), the most penetrating test liquid, were given a rating of 10.
  • Oil repellency The oil repellency of substrates was measured using the AATCC procedure, standard test method No. 118-1983. The oil repellency of the substrates are expressed in terms of the "OR" rating.
  • Dry soil resistance The dry soil resistance of substrates was measured using a method described in US 5,370,919. A value of 5 indicates that there is no increase in soiling versus an unsoiled sample. A dry soil rating of 1 indicates that the substrate was severely soiled.
  • Roll build up was measured by visually observing the amount of buildup on processing equipment during the production runs described in the examples. A scale of 0 to 5 was used to quantify the observed level of build up with 0 representing no visible build up and 5 representing severe build up. Values of 0 and 1 would represent very acceptable levels of roll build up.
  • PMA-2 A 1 1 blend of GenapolTM UD 080 with MEFOSA/AlfonicTM 6-8.5 that was prepared according to the procedure for the synthesis of fluorochemical F-18, in
  • OWR-1 A 50/50 blend of FC 398 and FC 399 ScotchgardTM Ca ⁇ et Protectors, 24% solids, both commercially available from 3M.
  • OWR-7 PAPI/ETHYLFOSE 1/3 prepared by heating PAPI and ETFOSE at 60°C in ethylacetate, until completion of isocyanate reaction.
  • the product was emulsified with Rew IM/OA (6% on solids) and Atpol E 5721 (2% on solids) at
  • FA 2820 Spin finish available from Zschimmer und Schwartz (Germany).
  • FA 2825 Spin finish available from Zschimmer und Schwartz (Germany).
  • LurolTM NF-6239-20 Spin finish available from Devan NV (Belgium).
  • LurolTM PP-3919 Spin finish available from Devan NV (Belgium). rpm Revolutions per minute Ex. Example
  • the amount of spin oil and fluorochemical applied to the yam was varied by adjusting the kiss roll speed and the concentration of the compounds in the spin finishing bath.
  • the ca ⁇ et yam was then drawn to about 3-4 times the extruded length to obtain a yam with a tex (weight (g)/1000 m) of about 165.
  • a hydrophilicity imparting compound was added to the extrudable composition. Without the use of a hydrophilicity imparting compound , a sticky layer was deposited on the guidance rolls of the cooling unit which caused major problems and delays in the production of treated yam.
  • the yam was textured at a temperature of about 140°C to 180°C to produce a bulked yam that would be particularly useful for ca ⁇ ets.
  • the bulked yam was visually inspected for mechanical quality after spinning and texturing and bulked yam made in accordance with the invention had no visible broken filaments.
  • yams were wrapped closely together around a piece of cardboard so there were no gaps between the yams and a flat surface comprising one layer of yam was obtained.
  • Examples 1 to 3 were made by using 0.4% PMA-1 as hydrophilicity imparting compound.
  • the spin finishing bath contained different amounts of FA 2820 and
  • This value represents the percentage of spin finish used in the spin finishing bath, not the residual amount of spin finish on the fiber.
  • Examples 1 and 2 had good dry soil values and acceptable oil and water repellencies.
  • Example 3 had rather low oil and water repellency values but a good dry soil resistance. Examples 4 to 11 and Comparative Examples C-2 to C-6
  • Examples 4 to 11 PP containing 0.45 % PMA-1 was extruded. Different spin finishes and amounts of OWR-1 were added to the spin finishing bath. Comparative Examples C-2 to C-6 were made with 0.45% PMA-1 in the melt, but without the use of any fluorochemical in the spin finishing bath. The amounts and types of spin finish and OWR-1 used, level of roll build up, oil and water repellencies and dry soil resistances, and fluorine content are given in Tables 3 and 4.
  • Examples 12 to 15 were made using various amounts of PMA-1.
  • the spin finishing bath contained different amounts of spin finish Lurol NF-6239-20 and 12% OWR-1.
  • the composition and extrusion parameters for the examples are reported in Table 5 and the fiber properties are reported in Table 6. In Comparative Example C-7, no PMA was added.
  • Table 5 Composition and Extrusion Parameters of Polypropylene Fibers
  • This value represents the percentage of spin finish used in the spin finishing bath, not the residual amount of spin finish on the fiber.
  • Examples 12 to 15 possessed reasonably acceptable oil and water repellent properties and good dry soil resistance values.
  • This value represents the percentage of spin finish used in the spin finishing bath, not the residual amount of spin finish on the fiber.
  • the data shows that the process of the invention can be optimized to minimize roll build up by proper selection of spin finish, spin finish level and PMA concentration.
  • PP fibers were extruded using 0.4% PMA-1.
  • the spin finishing bath contained 15% Lurol NF 6239-20 and the various fluorochemicals listed in Table 9. Comparative Example C-9 was made without hydrophilicity imparting compound or fluorochemical.
  • the composition of the fibers and roll build up values are set forth in Table 9 and the fiber properties are set forth in Table 10.
  • PMA-2 was used as hydrophilicity imparting compound, at concentrations of either 0.4 or 0.8% as indicated in Table 11.
  • the spin finishing bath contained 15% Lurol NF 6239-20 and the type and amount of fluorochemical given in Table 11.
  • the fiber compositions and roll build up values are presented in Table 11 and the fiber properties are presented in Table 12.
  • the data shows that roll build up and oil and water repellency can be optimized by proper selection of the type and amount of PMA and the type and amount of fluorochemical.
  • Examples 39 and 40 were made using 0.4% PMA-3.
  • the spin finishing bath contained 15% Lurol NF 6239-20 and the type and amounts of fluorochemical reported in Table 13.
  • the fiber compositions and roll build up values are reported in Table 13 and the fiber properties are reported in Table 14.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)

Abstract

La présente invention concerne un procédé permettant d'obtenir une fibre, consistant à: (a) procéder à l'extrusion par fusion d'un mélange renfermant un polymère thermoplastique et un composé favorisant l'hydrophilie pour former une pluralité de filaments, (b) exposer ces filaments à un ensimage de filature; et enfin, (c) procéder au filage de ces filaments en une fibre, l'ensimage de filature comprenant un composé fluoré. Cette invention concerne par ailleurs des fibres, des textiles et un tapis fabriqués selon le procédé de cette invention.
PCT/US1998/025517 1997-05-12 1998-12-02 Procede d'extrusion de fibres WO1999029936A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US09/554,528 US6426025B1 (en) 1997-05-12 1997-02-12 Process for extruding fibers
DE69817014T DE69817014T2 (de) 1997-12-05 1998-12-02 Extrusionsverfahren für fasern
JP2000524501A JP2001526326A (ja) 1997-12-05 1998-12-02 繊維を押し出す方法
AU16175/99A AU742193B2 (en) 1997-12-05 1998-12-02 Process for extruding fibers
EP98960619A EP1036223B1 (fr) 1997-12-05 1998-12-02 Procede d'extrusion de fibres

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP97203812.9 1997-12-05
EP97203812A EP0921216A1 (fr) 1997-12-05 1997-12-05 Procédé d'extrusion pour fibres

Publications (1)

Publication Number Publication Date
WO1999029936A1 true WO1999029936A1 (fr) 1999-06-17

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Country Status (6)

Country Link
EP (2) EP0921216A1 (fr)
JP (1) JP2001526326A (fr)
CN (1) CN1280635A (fr)
AU (1) AU742193B2 (fr)
DE (1) DE69817014T2 (fr)
WO (1) WO1999029936A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6537662B1 (en) 1999-01-11 2003-03-25 3M Innovative Properties Company Soil-resistant spin finish compositions
DE102014014479A1 (de) * 2014-04-16 2015-10-22 Perlon Nextrusion Monofil GmbH Monofilamente mit hoher Abrieb- und Formbeständigkeit, geringer Gleitreibung und Anschmutzneigung, textile Flächengebilde enthaltend diese und deren Verwendung
TWI623666B (zh) * 2016-11-30 2018-05-11 Modified water-repellent fiber and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0516271A1 (fr) * 1991-05-02 1992-12-02 Minnesota Mining And Manufacturing Company Fibre thermoplastique ayant propriétés hydrophiles durables
WO1997033019A1 (fr) * 1996-03-07 1997-09-12 Minnesota Mining And Manufacturing Company Fil pour moquette ayant une grande resistance aux salissures
WO1997044508A1 (fr) * 1996-05-21 1997-11-27 Minnesota Mining And Manufacturing Company Melanges de tensioactifs fluorochimiques et hydrocarbures utilises en qualite d'additifs hydrophiles dans des polymeres thermoplastiques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0516271A1 (fr) * 1991-05-02 1992-12-02 Minnesota Mining And Manufacturing Company Fibre thermoplastique ayant propriétés hydrophiles durables
WO1997033019A1 (fr) * 1996-03-07 1997-09-12 Minnesota Mining And Manufacturing Company Fil pour moquette ayant une grande resistance aux salissures
WO1997044508A1 (fr) * 1996-05-21 1997-11-27 Minnesota Mining And Manufacturing Company Melanges de tensioactifs fluorochimiques et hydrocarbures utilises en qualite d'additifs hydrophiles dans des polymeres thermoplastiques

Also Published As

Publication number Publication date
EP1036223B1 (fr) 2003-08-06
EP0921216A1 (fr) 1999-06-09
AU742193B2 (en) 2001-12-20
EP1036223A1 (fr) 2000-09-20
AU1617599A (en) 1999-06-28
JP2001526326A (ja) 2001-12-18
DE69817014D1 (de) 2003-09-11
DE69817014T2 (de) 2004-06-09
CN1280635A (zh) 2001-01-17

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